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United States Patent |
5,167,703
|
Eida
,   et al.
|
December 1, 1992
|
Ink, ink-jet recording process and instrument making use of the ink
Abstract
Provided is an ink comprising at least water, a water-soluble organic
solvent, and a dye, the dye comprising a compound represented by the
general formula (I):
##STR1##
wherein R.sub.1, R.sub.2, and R.sub.3 are respectively hydrogen or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1, or a
compound represented by the general formula (II):
##STR2##
wherein R.sub.1 is hydrogen, CH.sub.3, COOM, or SO.sub.3 M; R.sub.2 is
hydrogen, CH.sub.3, or COOM; R.sub.3 is hydrogen, chlorine, COOM, or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium, and m is 0 or 1.
Inventors:
|
Eida; Tsuyoshi (Yokohama, JP);
Yamamoto; Mayumi (Tokyo, JP);
Yamamoto; Takao (Isehara, JP)
|
Assignee:
|
Canon Kabushiki Kaisha (Tokyo, JP)
|
Appl. No.:
|
798948 |
Filed:
|
November 27, 1991 |
Foreign Application Priority Data
| Nov 30, 1990[JP] | 2-338758 |
| Nov 30, 1990[JP] | 2-338761 |
Current U.S. Class: |
106/31.52; 347/100; 534/680; 534/810; 534/811; 534/812; 534/815 |
Intern'l Class: |
C09D 011/02 |
Field of Search: |
106/22
534/680,810,811,812,815
346/1.1
|
References Cited
U.S. Patent Documents
4097476 | Jun., 1978 | Wicki | 534/815.
|
4426226 | Jan., 1984 | Ohta et al. | 106/22.
|
4557761 | Dec., 1985 | Kobayashi et al. | 106/22.
|
4592756 | Jun., 1986 | Kawasaki et al. | 106/22.
|
4661158 | Apr., 1987 | Kobayashi et al. | 106/22.
|
4670548 | Jun., 1987 | Westphal et al. | 534/811.
|
4734489 | Mar., 1988 | Kawasaki et al. | 106/22.
|
4737240 | Apr., 1988 | Davis et al. | 534/815.
|
4765838 | Aug., 1988 | Ohata et al. | 106/22.
|
4804411 | Feb., 1989 | Eida et al. | 106/22.
|
4841037 | Jun., 1989 | Ohta et al. | 106/22.
|
5017227 | May., 1991 | Koike et al. | 106/22.
|
5082496 | Jan., 1992 | Yamamoto et al. | 106/22.
|
Foreign Patent Documents |
0422668 | Apr., 1991 | EP.
| |
3619573 | Dec., 1986 | DE.
| |
Primary Examiner: Bell; Mark L.
Assistant Examiner: Klemanski; Helene
Attorney, Agent or Firm: Fitzpatrick, Cella, Harper & Scinto
Claims
What is claimed is:
1. An ink comprising at least water, a water-soluble organic solvent, and a
dye, the dye comprising a compound represented by the general formula (I):
##STR7##
wherein R.sub.1, R.sub.2, and R.sub.3 are respectively hydrogen or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
2. An ink according to claim 1, wherein one of R.sub.1, R.sub.2, and
R.sub.3 is SO.sub.3 M, m is 0, and two or three SO.sub.3 M groups in total
are included in the compound of the general formula (I).
3. An ink according to claim 1, wherein the ink contains the compound
represented by the general formula (I) in an amount of from 0.2 to 20% by
weight of the whole ink.
4. An ink according to claim 1, wherein the ink contains the water-soluble
organic solvent in an amount of from 2 to 50% by weight of the whole ink.
5. An ink according to claim 1, wherein the ink contains the water in an
amount of from 50 to 95 weight % of the whole ink.
6. An ink comprising at least water, a water-soluble organic solvent, and a
dye, the dye comprising a compound represented by the general formula
(II):
##STR8##
wherein R.sub.1 is hydrogen, CH.sub.3, COOM, or SO.sub.3 M; R.sub.2 is
hydrogen, CH.sub.3, or COOM; R.sub.3 is hydrogen, chlorine, COOM, or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
7. An ink according to claim 6, wherein none or one of R.sub.1, R.sub.2,
and R.sub.3 is SO.sub.3 M, none or one of R.sub.4, R.sub.5, R.sub.6,
R.sub.7, and R.sub.8 is SO.sub.3 M, m is 0, and two or three SO.sub.3 M
groups in total are included in the compound of the general formula (II).
8. An ink according to claim 6, wherein the ink contains the compound
represented by the general formula (II) in an amount of from 0.2 to 20% by
weight of the whole ink.
9. An ink according to claim 6, wherein the ink contains the water-soluble
organic solvent in an amount of from 2 to 50% by weight of the whole ink.
10. An ink according to claim 6, wherein the ink contains the water in an
amount of from 50 to 95 weight % of the whole ink.
11. An ink jet recording process of conducting recording by ejecting ink
droplets from an orifice in response to a recording signal, the ink
comprising at least water, a water-soluble organic solvent, and a dye, the
dye comprising a compound represented by the general formula (I):
##STR9##
wherein R.sub.1, R.sub.2, and R.sub.3 are respectively hydrogen or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
12. An ink jet recording process according to claim 11, wherein the ink
droplets are ejected by action of thermal energy.
13. An ink jet recording process according to claim 11, wherein one of
R.sub.1, R.sub.2, and R.sub.3 is SO.sub.3 M, m is 0, and two or three
SO.sub.3 M groups in total are included in the compound of the general
formula (I).
14. An ink jet recording process according to claim 11, wherein the ink
contains the compound represented by the general formula (I) in an amount
of from 0.2 to 20% by weight of the whole ink.
15. An ink jet recording process according to claim 11, wherein the ink
contains the water-soluble organic solvent in an amount of from 2 to 50%
by weight of the whole ink.
16. An ink jet recording process according to claim 11, wherein the ink
contains the water in an amount of from 50 to 95 weight % of the whole
ink.
17. An ink jet recording process according to claim 11, wherein the
recording is conducted on pigment-coated paper.
18. An ink jet recording process of conducting recording by ejecting ink
droplets from an orifice in response to a recording signal, the ink
comprising at least water, a water-soluble organic solvent, and a dye, the
dye comprising a compound represented by the general formula (II):
##STR10##
wherein R.sub.1 is hydrogen, CH.sub.3, COOM, or SO.sub.3 M; R.sub.2 is
hydrogen, CH.sub.3, or COOM; R.sub.3 is hydrogen, chlorine, COOM, or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
19. An ink jet recording process according to claim 18, wherein the ink
droplets are ejected by action of thermal energy.
20. An ink jet recording process according to claim 18, wherein none or one
of R.sub.1, R.sub.2, and R.sub.3 is SO.sub.3 M, none or one of R.sub.4,
R.sub.5, R.sub.6, R.sub.7, and R.sub.8 is SO.sub.3 M, m is 0, and two or
three SO.sub.3 M groups in total are included in the compound of the
general formula (II).
21. An ink recording process according to claim 18, wherein the ink
contains the compound represented by the general formula (II) in an amount
of from 0.2 to 20% by weight of the whole ink.
22. An ink jet recording process according to claim 18 wherein the ink
contains the water-soluble organic solvent in an amount of from 2 to 50%
by weight of the whole ink.
23. An ink jet recording process according to claim 18, wherein the ink
contains the water in an amount of from 50 to 95 weight % of the whole
ink.
24. An ink jet recording process according to claim 18, wherein the
recording is conducted on pigment-coated paper.
25. An ink jet device comprising an ink storing member impregnated with a
recording liquid, and a head having an orifice for ejecting the recording
liquid as droplets, the recording liquid comprising an ink containing at
least water, a water-soluble organic solvent, and a dye, the dye
comprising a compound represented by the general formula (I):
##STR11##
wherein R.sub.1, R.sub.2, and R.sub.3 are respectively hydrogen or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
26. An ink jet device according to claim 25, wherein the ink storing member
is an ink absorber or an ink bag.
27. An ink jet device according to claim 25, wherein the head has a heating
head to provide to the ink a heat energy for ejecting ink droplets.
28. An ink jet device according to claim 25, wherein one of R.sub.1,
R.sub.2, and R.sub.3 is SO.sub.3 M, m is 0, and two or three SO.sub.3 M
groups in total are included in the compound of the general formula (I).
29. An ink jet device according to claim 25, wherein the ink contains the
compound represented by the general formula (I) in an amount of from 0.2
to 20% by weight of the whole ink.
30. An ink jet device according to claim 25, wherein the ink contains the
water-soluble organic solvent in an amount of from 2 to 50% by weight of
the whole ink.
31. An ink jet device according to claim 25, wherein the ink contains the
water in an amount of from 50 to 95 weight % of the whole ink.
32. An ink jet device comprising an ink storing member impregnated with a
recording liquid, and a head having an orifice for ejecting the recording
liquid as droplets, the recording liquid comprising an ink containing at
least water, a water-soluble organic solvent, and a dye, the dye
comprising a compound represented by the general formula (II):
##STR12##
wherein R.sub.1 is hydrogen, CH.sub.3, COOM, or SO.sub.3 M; R.sub.2 is
hydrogen, CH.sub.3, or COOM; R.sub.3 is hydrogen, chlorine, COOM, or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
33. An ink jet device according to claim 32, wherein the ink storing member
is an ink absorber or an ink bag.
34. An ink jet device according to claim 32, wherein the head has a heating
head to provide to the ink a heat energy for ejecting ink droplets.
35. An ink jet device according to claim 32, wherein none or one of
R.sub.1, R.sub.2, and R.sub.3 is SO.sub.3 M, none or one of R.sub.4,
R.sub.5, R.sub.6, R.sub.7, and R.sub.8 is SO.sub.3 M, m is 0, and two or
three SO.sub.3 M groups in total are included in the compound of the
general formula (II).
36. An ink jet device according to claim 32, wherein the ink contains the
compound represented by the general formula (II) in an amount of from 0.2
to 20% by weight of the whole ink.
37. An ink jet device according to claim 32, wherein the ink contains the
water-soluble organic solvent in an amount of from 2 to 50% by weight of
the whole ink.
38. An ink jet device according to claim 32, wherein the ink contains the
water in an amount of from 50 to 95 weight % of the whole ink.
39. An ink jet recording apparatus comprising an ink jet device comprising
an ink storing member impregnated with a recording liquid, and a head
having an orifice for ejecting the recording liquid, the recording liquid
comprising an ink containing at least water, a water-soluble organic
solvent, and a dye, the dye comprising a compound represented by the
general formula (I):
##STR13##
wherein R.sub.1, R.sub.2, and R.sub.3 are respectively hydrogen or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
40. An ink jet recording apparatus according to claim 39, wherein the ink
storing member is an ink absorber or an ink bag.
41. An ink jet recording apparatus according to claim 39, wherein the head
has a heating head to provide to the ink a heat energy for ejecting ink
droplets.
42. An ink jet recording apparatus according to claim 39, wherein one of
R.sub.1, R.sub.2, and R.sub.3 is SO.sub.3 M, m is 0, and two or three
SO.sub.3 M groups in total are included in the compound of the general
formula (I).
43. An ink jet recording apparatus according to claim 39, wherein the ink
contains the compound represented by the general formula (I) in an amount
of from 0.2 to 20% by weight of the whole ink.
44. An ink jet recording apparatus according to claim 39, wherein the ink
contains the water-soluble organic solvent in an amount of from 2 to 50%
by weight of the whole ink.
45. An ink jet recording apparatus according to claim 39, wherein the ink
contains the water in an amount of from 50 to 95 weight % of the whole
ink.
46. An ink jet recording apparatus comprising an ink jet device comprising
an ink storing member impregnated with a recording liquid, and a head
having an orifice for ejecting the recording liquid, the recording liquid
comprising an ink containing at least water, a water-soluble organic
solvent, and a dye, the dye comprising a compound represented by the
general formula (II):
##STR14##
wherein R.sub.1 is hydrogen, CH.sub.3, COOM, or SO.sub.3 M; R.sub.2 is
hydrogen, CH.sub.3, or COOM; R.sub.3 is hydrogen, chlorine, COOM, or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
47. An ink jet recording apparatus according to claim 46, wherein the ink
storing member is an ink absorber or an ink bag.
48. An ink jet recording apparatus according to claim 46, wherein the head
has a heating head to provide to the ink a heat energy for ejecting ink
droplets.
49. An ink jet recording apparatus according to claim 46, wherein none or
one of R.sub.1, R.sub.2, and R.sub.3 is SO.sub.3 M, none or one of
R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 is SO.sub.3 M, m is 0, and
two or three SO.sub.3 M groups in total are included in the compound of
the general formula (II).
50. An ink jet recording apparatus according to claim 46, wherein the ink
contains the compound represented by the general formula (II) in an amount
of from 0.2 to 20% by weight of the whole ink.
51. An ink jet recording apparatus according to claim 46, wherein the ink
contains the water-soluble organic solvent in an amount of from 2 to 50%
by weight of the whole ink.
52. An ink jet recording apparatus according to claim 46, wherein the ink
contains the water in an amount of from 50 to 95 weight % of the whole
ink.
53. An ink cartridge comprising an ink bag impregnated with a recording
liquid comprising an ink, the ink containing at least water, a
water-soluble organic solvent, and a dye, the dye comprising a compound
represented by the general formula (I):
##STR15##
wherein R.sub.1, R.sub.2, and R.sub.3 are respectively hydrogen or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
54. An ink cartridge according to claim 53, wherein one of R.sub.1,
R.sub.2, and R.sub.3 is SO.sub.3 M, m is 0, and two or three SO.sub.3 M
groups in total are included in the compound of the general formula (I).
55. An ink cartridge according to claim 53, wherein the ink contains the
compound represented by the general formula (I) in an amount of from 0.2
to 20% by weight of the whole ink.
56. An ink cartridge according to claim 53, wherein the ink contains the
water-soluble organic solvent in an amount of from 2 to 50% by weight of
the whole ink.
57. An ink cartridge according to claim 53, wherein the ink contains the
water in an amount of from 50 to 95 weight % of the whole ink.
58. An ink cartridge comprising an ink bag impregnated with a recording
liquid comprising an ink, the ink containing at least water, a
water-soluble organic solvent, and a dye, the dye comprising a compound
represented by the general formula (II):
##STR16##
wherein R.sub.1 is hydrogen, CH.sub.3, COOM, or SO.sub.3 M; R.sub.2 is
hydrogen, CH.sub.3, or COOM; R.sub.3 is hydrogen, chlorine, COOM, or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
59. An ink cartridge according to claim 58, wherein none or one of R.sub.1,
R.sub.2, and R.sub.3 is SO.sub.3 M, none or one of R.sub.4, R.sub.5,
R.sub.6, R.sub.7, and R.sub.8 is SO.sub.3 M, m is 0, and two or three
SO.sub.3 M groups in total are included in the compound of the general
formula (II).
60. An ink cartridge according to claim 58, wherein the ink contains the
compound represented by the general formula (II) in an amount of from 0.2
to 20% by weight of the whole ink.
61. An ink cartridge according to claim 58, wherein the ink contains the
water-soluble organic solvent in an amount of from 2 to 50% by weight of
the whole ink.
62. An ink cartridge according to claim 58, wherein the ink contains the
water in an amount of from 50 to 95 weight % of the whole ink.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an ink, an ink jet recording method, and
an instrument employing the ink. More particularly, the present invention
relates to an ink which provides an excellent water-resistant printed
image on non-coated paper, and provides a printed image having improved
resistance against indoor discoloration on coated paper (paper having a
pigment-coating layer), and an ink jet recording process, an ink jet
device, an ink jet recording apparatus, and an ink cartridge employing the
above ink.
2. Related Background Art
A variety of ink compositions are hitherto known for ink jet recording. In
recent years, research and development have been comprehensively made
improve the composition and the properties of the ink to conduct
satisfactory recording on non-coated paper such as paper for copying,
paper for reporting, notebooks, letter paper, bond paper, continuous
business forms, and the like.
For example, inks involve the problems as below. Inks generally contain a
high-boiling organic solvent such as glycol for prevention of drying-up
and clogging. When printing is conducted on a recording medium with such
an ink, the printed image run and become blurred, or scraped caused by
sweat, a water drop, or the like, since the coloring matter used in the
ink is a water-soluble dye. Further, full-color images which are printed
on coated paper for forming the image clearly, come to be discolored
disadvantageously even in a room where the direct sun light illumination
is excluded, although sufficient light-fastness and weatherability are
required to the color images.
SUMMARY OF THE INVENTION
The present invention intends to provides an ink which provides printed
images with sufficient durability on non-coated paper, and provides
printed images with little discoloration on coated paper.
The present invention further provides an ink jet recording method and an
instrument employing the ink.
The present invention provides an ink comprising at least water, a
water-soluble organic solvent, and a dye, the dye comprising a compound
represented by the general formula (I):
##STR3##
wherein R.sub.1, R.sub.2, and R.sub.3 are respectively hydrogen or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
The present invention also provide an ink comprising at least water, a
water-soluble organic solvent, and a dye, the dye comprising a compound
represented by the general formula (II):
##STR4##
wherein R.sub.1 is hydrogen, CH.sub.3, COOM, or SO.sub.3 M; R.sub.2 is
hydrogen, CH.sub.3, or COOM; R.sub.3 is hydrogen, chlorine, COOM, or
SO.sub.3 M; R.sub.4 is hydrogen, OCH.sub.3, NH.sub.2, NHCONH.sub.2, or
SO.sub.3 M; R.sub.5 is hydrogen or SO.sub.3 M; R.sub.6 is hydrogen or
NH.sub.2 ; R.sub.7 is hydrogen, CH.sub.3, or OCH.sub.3 ; R.sub.8 is
hydrogen, COOM, or SO.sub.3 M; R.sub.5 is hydrogen and R.sub.8 is COOM
when both of R.sub.4 and R.sub.6 are respectively NH.sub.2 ; M is an
alkali metal, ammonium, or organic ammonium; and m is 0 or 1.
The present invention still also provides an ink jet recording process for
conducting recording by ejecting ink droplets from an orifice in response
to a recording signal, wherein the ink as described above is used.
The present invention further provides an ink jet device comprising an ink
storing member impregnated with a recording liquid, and a head having an
orifice for ejecting the recording liquid as droplets, wherein the ink as
described above is used.
The present invention still further provides an ink jet recording apparatus
comprising an ink jet device comprising an ink storing member impregnated
with a recording liquid, and a head having an orifice for ejecting the
recording liquid, wherein the ink as described above is used.
The present invention still further provides an ink cartridge comprising an
ink bag impregnated with a recording liquid comprising an ink, wherein the
ink as described above is used.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A and FIG. 1B illustrate a longitudinal cross section and a
transverse cross section, respectively, of a head of an ink jet recording
apparatus.
FIG. 2 is a perspective illustration of the appearance of a head having a
multiple set of the heads as shown in FIG. 1A and 1B.
FIG. 3 is a perspective illustration of an example of an ink jet recording
apparatus.
FIG. 4 is a longitudinal cross-sectional illustration of an ink cartridge.
FIG. 5 is a perspective illustration of a recording device.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments are described below in detail.
The present invention is characterized mainly by use of a dye having a
specified structure as the coloring material of ink, thereby providing an
ink which gives durable printed images on various non-coated paper and
gives less discoloring images on coated paper, and providing also an ink
jet recording method and instruments employing the ink.
The dyes represented by the general formulae (I) and (II), which are used
in the present invention and mainly characterizing the present invention,
include any of the dyes of the above general formulae, and may be used
singly or in combination of two or more thereof. Further, the dye may be
used in combination with another dye which is not included in the dyes of
the above general formulae.
Among the dyes of the general formula (I), particularly preferred are those
shown below:
##STR5##
Among the dyes of the general formula (II), particularly preferred are
those shown below:
##STR6##
Among the dyes shown above, particularly preferred ones, in view of the
effect of the present invention, are the compounds represented by the
general formula (I) in which one of R.sub.1, R.sub.2, and R.sub.3 is
SO.sub.3 M, m is 0, and two or three SO.sub.3 M groups in total are
contained, and the compounds represented by the general formula (II) in
which none or one of R.sub.1, R.sub.2, and R.sub.3 is SO.sub.3 M, none or
one of R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 is SO.sub.3 M, m is
0, and two or three SO.sub.3 M groups in total are contained.
The content of the dye in the ink depends on the kinds of the components of
the liquid medium and the properties required to the ink. Generally, the
content is in the range of from about 0.2 to about 20% by weight,
preferably from 0.5 to 10% by weight, more preferably from 1 to 5% by
weight of the whole ink.
The liquid medium used in the present invention is a mixture of water and a
water-soluble organic solvent. The water may be ordinary water but is
preferably deionized water. The organic solvent includes alkyl alcohols
having 1 to 5 carbons such as methyl alcohol, ethyl alcohol, n-propyl
alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl
alcohol, isobutyl alcohol, n-pentanol, etc., and halogenated derivatives
thereof; amides such as dimethylformamide, dimethylacetamide, etc.;
ketones and ketoalcohols such as acetone, diacetone alcohol, etc.; ethers
such as tetrahydrofuran, dioxane, etc.; oxyethylene or oxypropylene
addition products such as diethylene glycol, triethylene glycol,
tetraethylene glycol, dipropylene glycol, tripropylene glycol,
polyethylene glycol, polypropylene glycol, etc.; alkylene glycols having
alkylene group of 2 to 6 carbons such as ethylene glycol, propylene
glycol, trimethylene glycol, butylene glycol, 1,2,6-hexane triol, hexylene
glycol, etc.; thiodiglycol; glycerin; ethers of a polyhydric alcohol with
a lower alkyl such as ethylene glycol monomethyl (or monoethyl) ether,
diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol
monomethyl (or monoethyl) ether, etc.; diethers of a polyhydric alcohol
with a lower alkyl such as triethylene glycol dimethyl (or diethyl) ether,
tetraethylene glycol dimethyl (or diethyl) ether, etc.; sulfolane,
N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like.
The content of the aforementioned water soluble organic solvent is
generally in the range of from 2 to 50%, preferably 2 to 30% by weight of
the whole ink. The solvent may be used singly or in combination of two or
more thereof.
The main constituents of the ink of the present invention is described
above. Other additives such as a dispersant, a surfactant, a viscosity
controlling agent, a surface tention controlling agent, a fluorescent
whitening agent, and the like may be added to the ink, if necessary,
within the range that the object of the present invention is achieved. The
examples are viscosity controlling agents such as polyvinyl alcohol,
cellulose derivatives; various surface active agents of cation type, anion
type, and nonion type; surface tension controlling agents such as
diethanolamine, and triethanolamine; pH controlling agents such as buffer
solutions; mildewproofing agents; and the like.
For formulation of the ink used for ink jet recording which gives electric
charge to the ink, there is added a resistivity controlling agent such as
inorganic salts including lithium chloride, ammonium chloride, sodium
chloride.
The ink of the present invention is particularly suitable for an ink jet
recording method of recording by ejecting ink droplets by a bubbling
phenomenon upon thermal energy, and has the characteristic of stabilizing
the ink ejection without causing satellite dots or other disadvantages. In
this case, thermal properties such as specific heat, thermal expansion
coefficient, and thermal conductivity may be adjusted, if necessary.
The ink itself of the present invention is desirably adjusted to have a
surface tension at 25.degree. C. of from 30 to 68 dyne/cm, and a viscosity
at 25.degree. C. of not more than 15 cP, preferably not more than 10 cP,
more preferably not more than 5 cP for the purpose of solving the problems
of running of the ink, drying property of recorded images, and
permeability of ink on non-coated paper or other recording mediums, and
for the purpose of improving the matching of the ink with an ink jet head.
In order to adjust the properties of the ink as above and to solve the
problems in recording on non-coated paper, the water content in the ink of
the present invention made to be in the range of from 50 to 95% by weight,
preferably from 60 to 90% by weight.
The ink of the present invention, which is particularly suitable for an ink
jet recording method for recording by ejecting ink droplets by thermal
energy, is naturally useful also for general writing utensils.
The methods and the apparatus suitable for the use of the ink of the
present invention are those that provide thermal energy to ink in a cell
in a recording head in correspondence with recording signals to form ink
droplets by the thermal energy.
An example of the constitution of the heads, which is a main portion of the
apparatus, is shown in FIG. 1A, FIG. 1B, and FIG. 2.
A head 13 is formed by bonding a plate of glass, ceramics, or plastics
having a groove 14 with a heat-generating head 15. (The type of the head
is not limited to the one shown in the drawing.) The heat-generating head
15 is constituted of a protection layer 16 formed of silicon oxide or the
like, aluminum electrodes 17-1 and 17-2, a heat-generating resistance
layer 18 formed of nichrome or the like, a heat accumulation layer 19, and
a substrate plate 20 having heat-releasing property made of alumina or the
like.
Ink 21 reaches the ejection orifice 22 (a fine pore), forming a meniscus by
action of pressure P not shown in the figure.
On application of an electric signal to the electrodes 17-1 and 17-2, the
region designated by a symbol "n" on the heat-generation head 15 abruptly
generates heat to form a bubble in the ink 21 at the position adjacent
thereto. The pressure generated by the bubble pushes out the meniscus 23
and ejects the ink 21, as recording droplet 24, and the ink droplets are
propelled to a recording medium 25. FIG. 2 illustrates exterior appearance
of a multi-head constructed by juxtaposing a multiplicity of heads shown
in FIG. 1A. The multi-head is prepared by bonding a glass plate having
multi-grooves with a heat-generation head 28 similar to the one described
in FIG. 1A.
Incidentally, FIG. 1A is a cross-sectional view of the head 13 along an ink
flow path, and FIG. 1B is a cross-sectional view of the head at the line
A-B in FIG. 1A.
FIG. 3 illustrates an example of the ink-jet recording apparatus having
such a head mounted therein.
In FIG. 3, a blade 61 as a wiping member is held at one end by a
blade-holding member, forming a fixed end in a shape of a cantilever. The
blade 61 is placed at a position adjacent to the recording region of the
recording head, and in this example, is held so as to protrude into the
moving path of the recording head. A cap 62 is placed at a home position
adjacent to the blade 61, and is constituted such that it moves in the
direction perpendicular to the moving direction of the recording head to
come into contact with the ejection nozzle face to cap the nozzles. An ink
absorption member 63 is provided at a position adjacent to the blade 61,
and is held so as to protrude into the moving path of the recording head
in a manner similar to that of the blade 61. The aforementioned blade 61,
the cap 62, the absorption member 63 constitute an ejection-recovery
section 64, the blade 61 and the absorption member 63 remove water, dust,
and the like from the ink ejecting nozzle face.
A recording head 65 has an ejection energy generation means for ejection,
and conducts recording by ejecting ink toward a recording medium opposing
to the ejection nozzle face. A carriage 66 is provided for supporting and
moving the recording head 65. The carriage 66 is engaged slideably with a
guide rod 67. A portion of the carriage 66 is connected (not shown in the
figure) to a belt 69 driven by a motor 68, so that the carriage 66 is
movable along the guide rod 67 to the recording region of the recording
head and the adjacent region thereto.
The constitution of a paper delivery portion 51 for delivery of a recording
medium and a paper delivery roller 52 driven by a motor not shown in the
figure delivers the recording medium to the position opposing to the
ejecting nozzle face of the recording head, and the recording medium is
discharged with the progress of the recording to paper discharge portion
provided with paper-discharge rollers 53.
In the above constitution, the cap 62 of the ejection-recovery portion 64
is out of the moving path of the recording head 65, while the blade 61 is
made to protrude into the moving path. Therefore, the ejecting nozzle face
of the recording head 65 is wiped therewith. The cap 62 moves to protrude
toward the moving path of the recording head when the cap 62 comes into
contact for capping with the ejecting nozzle face of the recording head.
At the time when the recording head 65 moves from the home position to the
record-starting position, the cap 62 and the blade 61 are at the same
position as in the above-mentioned wiping time, so that the ejection
nozzle face of the recording head is wiped also in this movement.
The recording head moves to the home position not only at the end of the
recording and at the time of ejection recovery, but also at a
predetermined interval during movement for recording in the recording
region. By such movement, the wiping is conducted.
FIG. 4 illustrates an example of the ink cartridge containing ink to be
supplied through an ink supplying member such as a tube. The ink container
portion 40, for example an ink bag, contains an ink to be supplied, and
has a rubber plug 42 at the tip. By inserting a needle (not shown in the
drawing) into the plug 42, the ink in the ink bag 40 becomes suppliable.
An absorption member 44 absorbs waste ink.
The ink container portion has preferably a liquid-contacting face made of
polyolefin, especially polyethylene in the present invention.
The ink-jet recording apparatus used in the present invention is not
limited to the above-mentioned one which has separately a head and an ink
cartridge. Integration thereof as shown in FIG. 5 may suitably be used.
In FIG. 5, a recording device 70 houses an ink container portion such as an
ink absorption member, and the ink in the ink absorption member is ejected
from a head 71 having a plurality of orifices. The material for the ink
absorption member is preferably polyurethane in the present invention.
Air-communication opening 72 is provided to communicate the interior of the
cartridge with the open air.
The recording device 70 may be used in place of the recording head shown in
FIG. 3, and is readily mountable to and demountable from the carriage 66.
The present invention is described in more detail referring to example and
comparative examples. The "part(s)" and "%" in the description are based
on weight unless otherwise mentioned.
EXAMPLES 1 to 10 and COMPARATIVE EXAMPLES 1 and 2
The components shown below were mixed and dissolved, and the resulting
solution was filtered under pressure through a filter having pores of 1
.mu.m in diameter to obtain the inks of the examples and the comparative
examples as shown in Table 1.
TABLE 1
______________________________________
Example 1
Diethylene glycol 25 parts
Pure water 72 parts
Exemplified dye I-(1) 3 Parts
Example 2
Diethylene glycol 30 parts
Pure water 67 parts
Exemplified dye I-(2) 3 Parts
Example 3
Ethylene glycol 20 parts
Pure water 76 parts
Exemplified dye I-(4) 4 Parts
Example 4
Glycerin 20 parts
Pure water 75 parts
Exemplified dye I-(6) 5 parts
Example 5
Triethylene glycol 25 parts
Ethylene glycol monomethyl ether
15 parts
Pure water 55 part
Exemplified dye I-(9) 5 Parts
Example 6
Glycerin 20 pars
Pure water 76 parts
Exemplified dye I-(10)
4 Parts
Example 7
Glycerin 15 parts
N-methyl-2-pyrrolidone
10 parts
Pure water 71 parts
Exemplified dye I-(13)
4 Parts
Example 8
Triethylene glycol 20 parts
Ethylene glycol monomethyl ether
15 parts
Pure water 60 parts
Exemplified dye I-(14)
5 Parts
Example 9
Ethylene glycol 25 parts
N-methyl-2-pyrrolidone
10 parts
Pure water 61 parts
Exemplified dye I-(15)
4 Parts
Example 10
Diethylene glycol 25 parts
Polyethylene glycol 10 parts
N,N-dimethylimidazolidinone
5 parts
Pure water 57 parts
Exemplified dye I-(18)
3 Parts
Comparative Example 1
Diethylene glycol 30 parts
Pure water 67 parts
C. I. Food Black 1 3 Parts
Comparative Example 2
Ethylene glycol 20 parts
Pure water 76 parts
C. I. Food Black 2 4 Parts
______________________________________
With the inks of the above Examples 1 to 10, solid printing was conducted
by means of a recording apparatus (BJ-130, made by Canon K.K.) having an
On-Demand type of multiple orifice head for conducting recording by giving
heat energy to the ink in the recording head to form liquid droplets, thus
preparing printed pieces in the size of 10.times.20 mm. The test paper
used were paper recommended for Canon NP-6150, Canon NP-Dry,
Noizidlerpaper, and Proberbond paper. The optical densities of the printed
matters were all within the range of from 1.30 to 1.45. The water
resistance of the print was evaluated by immersing the printed piece in
stagnant water at 20.degree. C. for 5 minutes and then measuring the
degree of decrease of the optical density. All of the printed pieces
exhibited the degree of the decrease of not more than 15%, and was
sufficiently water-resistant. On the other hand, the inks of Comparative
Examples 1 and 2 were tested for the water resistance in the same manner
as above. The degree of decrease of the optical density was not less than
50% for all samples.
Further, printing was conducted on specified paper for Canon Color Bubble
Jet Copier in the same manner as above, and the printed matter was kept
standing in a test chamber in which ozone concentration was being
maintained at 30 ppm for 2 hours. The color difference (.DELTA.E*ab)
caused by the standing in the test chamber was measured. The evaluation
results are graded by the standards as below:
.largecircle.: .DELTA.E*ab<5
.DELTA.: 5.ltoreq..DELTA.E*ab.ltoreq.10
x: .DELTA.E*ab>10
The printed matters prepared with the inks of Examples 1 to 10 were all
evaluated as .largecircle. (.DELTA.E*ab<5), showing no remarkable
discoloration. On the contrary, that of Comparative Example 1 was
evaluated as .DELTA., showing relatively slight discoloration, but that of
Comparative Example 2 was evaluated as x, showing significant
discoloration.
EXAMPLES 11 to 20 and COMPARATIVE EXAMPLES 3 and 4
The components shown below were mixed and dissolved, and the resulting
solution was filtered under pressure through a filter having pores of 1
.mu.m in diameter to obtain the inks of the examples and the comparative
examples as shown in Table 2.
TABLE 2
______________________________________
Example 11
Diethylene glycol 30 parts
Pure water 67 parts
Exemplified dye II-(1)
3 parts
Example 12
Ethylene glycol 25 parts
Pure water 71 parts
Exemplified dye II-(3)
4 Parts
Example 13
Glycerin 15 parts
Pure water 82 parts
Exemplified dye II-(5)
3 Parts
Example 14
Diethylene glycol 20 parts
Pure water 76 parts
Exemplified dye II-(6)
4 Parts
Example 15
Triethylene glycol 20 parts
N-methyl-2-pyrrolidone
10 parts
Pure water 65 parts
Exemplified dye II-(8)
5 parts
Example 16
Glycerin 20 parts
Pure water 77 parts
Exemplified dye II-(10)
3 Parts
Example 17
Polyethylene glycol 300
20 parts
Glycerin 10 parts
Pure water 66 parts
Exemplified dye II-(11)
4 Parts
Example 18
Diethylene glycol 25 parts
Ethylene glycol monomethyl ether
10 parts
Pure water 60 parts
Exemplified dye II-(13)
5 Parts
Example 19
Ethylene glycol 30 parts
N-methyl-2-pyrrolidone
5 parts
Pure water 61 parts
Exemplified dye II-(16)
4 parts
Example 20
Triethylene glycol 25 parts
Glycerin 10 parts
N,N-dimethylimidazolidinone
5 parts
Pure water 55 parts
Exemplified dye II-(18)
5 parts
Comparative Example 3
Diethylene glycol 30 parts
Pure water 65 parts
C. I. Food Black 1 5 Parts
Comparative Example 4
Triethylene glycol 25 parts
Pure water 71 parts
C. I. Food Black 2 4 Parts
______________________________________
With the inks of the above Examples 11 to 20, solid printing was conducted
by means of a recording apparatus (BJ-130, made by Canon K.K.) having an
On-Demand type of multiple orifice head for conducting recording by giving
heat energy to the ink in the recording head to form liquid droplets, thus
preparing printed pieces in the size of 10.times.20 mm. The test papers
used were papers recommended for Canon NP-6150, Canon NP-Dry,
Noizidlerpaper, and Proberbond paper. The optical densities of the printed
matters were all within the range of from 1.30 to 1.45. The water
resistance of the print was evaluated by immersing the printed piece in
stagnant water at 20.degree. C. for 5 minutes and then measuring the
degree of decrease of the optical density. All of the printed pieces
exhibited the degree of the decrease of not more than 15%, and was
sufficiently water-resistant. On the other hand, the inks of Comparative
Examples 3 and 4 were tested for the water resistance in the same manner
as above. The degree of decrease of the optical density was not less than
50% for all samples.
Further, printing was conducted on specified paper for Canon Color Bubble
Jet Copier in the same manner as above, and the printed matter was kept
standing in a test chamber in which ozone concentration was being
maintained at 30 ppm for 2 hours. The color difference (.DELTA.E*ab)
caused by the standing in the test chamber was measured. The evaluation
results are graded by the standards as below:
.largecircle.: .DELTA.E*ab<5
.DELTA.: 5.ltoreq..DELTA.E*ab.ltoreq.10
x: .DELTA.E*ab>10
The printed matters prepared with the inks of Examples 11 to 20 were all
evaluated as .largecircle. (.DELTA.E*ab<5), showing no remarkable
discoloration. On the contrary, that of Comparative Example 3 was
evalutated as .DELTA., showing relatively slight discoloration, but that
of Comparative Example 4 was evaluated as x, showing significant
discoloration.
EXAMPLE 21
Inks (a) to (e) were prepared in the same manner as in Example 1 except
that the dyes were changed respectively to the mixture having the
composition as below.
______________________________________
(a): I-(1) 1.5 parts
II-(6) 1.5 parts
(b): I-(5) 1.8 parts
II-(12) 1.2 parts
(c): I-(8) 2.0 parts
II-(4) 1.0 part
(d): I-(8) 2.0 parts
II-(10) 1.0 part
(e): I-(17) 1.0 part
II-(2) 2.0 parts
______________________________________
With these inks, printing was conducted on the aforementioned kinds of
paper by means of the above recording apparatus BJ-130. The
water-resistance was evaluated in the same manner as above, and was found
that the degree of decrease of the optical density was not more than 15%
for all the printed pieces. The discoloration by ozone was evaluated as
above and was found that the .DELTA.E*ab value was less than 5 for all the
printed pieces. Further, the printed pieces were exposed to indoor light
for 6 months, and found that the color change after the 6 month exposure
was less than 5 in terms of .DELTA.E*ab.
EXAMPLE 22
The aforementioned printed matters of Examples 1 to 20 prepared by printing
on specified paper for Canon Color-Bubble Jet Copier coated paper (made by
Canon Inc., designated paper for BJ-A1) with the copying apparatus BJ-130
were tested for light-fastness by exposing light for 100 hours by Xenon
fade-o-meter (made by Atlas Co.). The degree of decrease of the optical
density was not higher than 30% for all the samples. On the contrary, that
for the Comparative Examples 1 and 3 was higher than 60%.
Further, the discoloration of the above printed matters after 6 months of
exposure to indoor light was less than 5 in terms of .DELTA.E*ab, while
that of Comparative Examples 2 and 4 was both more than 10.
From the description above, it is clear that inks which provides printed
matters having light-fastness on non-coated paper or which provides
printed matters having resistance to discoloration on coated paper are
provided by selecting the dye having the specified structure as the
coloring matter according to the present invention.
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